TW201634567A - 以聚碳酸酯為基礎之樹脂組成物及其模製物 - Google Patents
以聚碳酸酯為基礎之樹脂組成物及其模製物 Download PDFInfo
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- TW201634567A TW201634567A TW104140774A TW104140774A TW201634567A TW 201634567 A TW201634567 A TW 201634567A TW 104140774 A TW104140774 A TW 104140774A TW 104140774 A TW104140774 A TW 104140774A TW 201634567 A TW201634567 A TW 201634567A
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Abstract
本發明關於一種以聚碳酸酯為基礎之樹脂組成物及其模製物,且更具體地說,關於其衝擊強度、流動性等經改良的以聚碳酸酯為基礎之樹脂組成物,及其模製物。
Description
本申請案主張於2014年12月4日向韓國智慧財產局(Korean Intellectual Property Office)申請之韓國專利申請案第10-2014-0173005號的優先權及權益,該申請案之全部內容以引用方式併入本文中。
本發明關於一種以聚碳酸酯為基礎之樹脂組成物及其模製物,且更具體地說,關於其衝擊強度、流動性等經改良的以聚碳酸酯為基礎之樹脂組成物,及其模製物。
聚碳酸酯樹脂係藉由芳族二醇諸如雙酚A與碳酸酯前驅物諸如光氣之縮合聚合而製備並具有極佳衝擊強度、尺寸穩定性、耐熱性、及透明性等。因此,聚碳酸酯樹脂具有在廣泛用途上的應用,諸如電氣和電子產品、汽車零件、建築材料、及光學元件等的外部材料。
最近,為了將這些聚碳酸酯樹脂應用至更多不同的領域,已經進行了許多研究,以藉由共聚合二或多種彼此具有不同結構的芳族二醇化合物並將具有不同結構的單元引入聚碳酸酯的主鏈來獲得所要的物理性質。此外,已進行對於聚碳酸酯的主鏈中引入聚矽氧烷結構的研究,但大多數這些技術具有的缺點在於:當特定物理性質得到改良,但其他物理性質劣化。
同時,最近,因使用聚碳酸酯樹脂形成薄膜的需求已增加,而對於在熔融方法期間具有高流動性和因此具有極佳熔融加工性之以聚碳酸酯為基礎之樹脂,或其組成物之需求已增加。此外,最近,對於聚碳酸酯樹脂中所需要之各種物理性質諸如耐化學性、衝擊強度、或類似者的要求進一步提高。
然而,通常,在進一步改良以聚碳酸酯為基礎之樹脂或其組成物的耐化學性、衝擊強度、或類似者之情況下,流動性可能被惡化,致使難以充分達成薄膜模塑性和熔融加工性。因此,難以滿足以聚碳酸酯為基礎之樹脂中所需要之高流動性和熔融流動性以呈現極佳薄膜模塑性、或類似者,且同時具有極佳耐化學性、衝擊強度等。
因此,持續需要其衝擊強度諸如低溫衝擊強度、或類似者、流動性、熔融加工性等被同時改良的以聚碳酸酯為基礎之樹脂,或其組成物。
本發明已努力於提供一種具有改良之衝擊強度、流動性、加工性、等等的以聚碳酸酯為基礎之樹脂組成物。
本發明已努力於提供含有以聚碳酸酯為基礎之樹脂組成物的模製物。
本發明之一示例性實施態樣提供一種以聚碳酸酯為基礎之樹脂組成物,其包含:共聚碳酸酯樹脂,其包括以下示化學式1表示之重複單元、以下示化學式3表示之重複單元、及以下示化學式4表示之重複單元;及第一聚碳酸酯樹脂,其包括以下示化學式2表示之重複單元:
在化學式1中,R1至R4各自獨立地為氫、C1-10烷基、C1-10烷氧基、或鹵素,及,Z1為未經取代或經苯基取代之C1-10伸烷基、未經取代或經C1-10烷基取代之C3-15伸環烷基、O、S、SO、SO2、或CO,
在化學式2中,R5至R12各自獨立地為氫、C1-10烷基、C1-10烷氧基、或鹵素,Z2和Z3各自獨立地為未經取代或經苯基取代之C1-10伸烷基、未經取代或經C1-10烷基取代之C3-15伸環烷基、O、S、SO、SO2、或CO,及A為C1-15伸烷基,
在化學式3中,各X1獨立地為C1-10伸烷基,各R13獨立地為氫;未經取代或經環氧乙烷基、經環氧乙烷基取代之C1-10烷氧基、或C6-20芳基取代之C1-15烷基;鹵素;C1-10烷氧基;烯丙基;C1-10鹵烷基;或C6-20芳基,及n為10至200的整數,
在化學式4中,各X2獨立地為C1-10伸烷基,各Y1獨立地為氫、C1-6烷基、鹵素、羥基、C1-6烷氧基或C6-20芳基,各R14獨立地為氫;未經取代或經環氧乙烷基、經環氧乙烷基取代之C1-10烷氧基、或C6-20芳基取代之C1-15烷基;鹵素;C1-10烷氧基;烯丙基;C1-10鹵烷基;或C6-20芳基,及m為10至200的整數。
本發明之另一示例性實施態樣提供模製物,其含有以聚碳酸酯為基礎之樹脂組成物。
以下,將更詳細地描述根據本發明之示例性實施態樣的以聚碳酸酯為基礎之樹脂組成物及其模製物。
本文所使用之專業術語僅用於描述特定實施態樣,且不限制本發明。此外,本說明書中所使用之單數形式包括複數形式,只要它們沒有明確不同的意義。
另外,本說明書中所使用之術語‘包括’或‘含有’係指定特定性質、區域、整數、步驟、操作、因子、及/或成
分,但不排除存在或附加一或多個其它特定性質、區域、整數、步驟、操作、成分及/或基團。
根據本發明之示例性實施態樣,提供一種以聚碳酸酯為基礎之樹脂組成物,其包含:共聚碳酸酯樹脂,其包括以下示化學式1表示之重複單元、以下示化學式3表示之重複單元、和以下示化學式4表示之重複單元;及第一聚碳酸酯樹脂,其包括以下示化學式2表示之重複單元:
在化學式1中,R1至R4各自獨立地為氫、C1-10烷基、C1-10烷氧基、或鹵素,及Z1為未經取代或經苯基取代之C1-10伸烷基、未經取代或經C1-10烷基取代之C3-15伸環烷基、O、S、SO、SO2、或CO,
在化學式2中,R5至R12各自獨立地為氫、C1-10烷基、C1-10烷氧基、或鹵素,Z2和Z3各自獨立地為未經取代或經苯基取代之C1-10伸烷基、未經取代或經C1-10烷基取代之C3-15伸環烷基、O、S、SO、SO2、或CO,及A為C1-15伸烷基,
在化學式3中,各X1獨立地為C1-10伸烷基,各R13獨立地為氫;未經取代或經環氧乙烷基、經環氧乙烷基取代之C1-10烷氧基、或C6-20芳基取代之C1-15烷基;鹵素;C1-10烷氧基;烯丙基;C1-10鹵烷基;或C6-20芳基,及n為10至200的整數,
在化學式4中,各X2獨立地為C1-10伸烷基,各Y1獨立地為氫、C1-6烷基、鹵素、羥基、C1-6烷氧基或C6-20芳基,各R14獨立地為氫;未經取代或經環氧乙烷基、經環氧乙烷基取代之C1-10烷氧基、或C6-20芳基取代之C1-15烷基;鹵素;C1-10烷氧基;烯丙基;C1-10鹵烷基;或C6-20芳基,及m為10至200的整數。
第一聚碳酸酯樹脂除了以化學式2表示之重複單元之外,可選擇性地另外包括以化學式1表示之重複單元。共聚碳酸酯樹脂中所包括的以化學式1表示之重複單元可具有等於或不同於以化學式1表示之重複單元的結構。
如上所述,根據示例性實施態樣之樹脂組成物可包括下列二者:第一聚碳酸酯樹脂,其具有包括脂族伸烷基A基團的以化學式2表示之重複單元,和共聚碳酸酯樹脂,其包括以化學式3和4表示之重複單元的含特定聚矽氧烷,與以化學式1表示之重複單元(其為一般芳族聚碳酸酯之重複單元)一起。將描述於下之第一聚碳酸酯樹脂和第二聚碳酸酯樹脂與共聚碳酸酯樹脂之區別可在於:聚矽氧烷結構係不引入第一和第二聚碳酸酯樹脂之主鏈中,而是引入共聚碳酸酯樹脂之主鏈中,如在化學式3和4中。以下,除非特別說明,否則第一和第二聚碳酸酯樹脂和共聚碳酸酯樹脂可區別且如上所述定義。
具有以化學式2表示之重複單元的第一聚碳酸酯樹脂藉由含有具有脂族基團A之重複單元可使根據示例性實施態樣之樹脂組成物具有較高流動性。另外,本發明人連續實驗的結果,可確認具有以化學式3和4表示之重複單元的共聚碳酸酯樹脂藉由含有特定聚矽氧烷基團可使低根據示例性實施態樣之樹脂組成物具有改良之衝擊強度(特別是,低溫衝擊強度)和耐化學性及低黃色指數(YI)值。
因此,可確認當根據示例性實施態樣之樹脂組成物同時包括具有此等特定重複單元結構之第一聚碳酸酯樹脂和共聚碳酸酯樹脂時,樹脂組成物可具有極佳流動性和熔融流動性,從而具有極佳薄膜模塑性,及其模製物可具有極佳耐化學性、極佳衝擊強度諸如低溫衝擊強度、或類似者,及低YI值。因此,根據示例性實施態樣之樹脂組成物可解決在該項領域中已知的以聚碳酸酯為基礎之樹脂的問題,或類似者,及適當地應用於其中需要極佳物理性質及薄膜模製之各種領域和用途。
以下,將詳細地描述各個能夠包括在根據本發明之示例性實施態樣的以聚碳酸酯為基礎之樹脂組成物中的成分。
(1)共聚碳酸酯樹脂
共聚碳酸酯樹脂,其為能夠改良現有芳族聚碳酸酯樹脂之物理性質(特別是,衝擊強度、耐化學性、YI值、等等)之成分,可包括在根據示例性實施態樣之樹脂組成物
中。共聚碳酸酯樹脂可包括以化學式1表示之重複單元,其為芳族以聚碳酸酯為基礎之樹脂的基本重複單元,及以化學式3和4表示之重複單元,其具有特定聚矽氧烷單元。
首先,形成共聚碳酸酯樹脂之基本骨架的以化學式1表示之重複單元可藉由芳族二醇化合物和碳酸酯前驅物的反應形成。如上所述之以化學式1表示之重複單元也可包括在將描述於下之第一和第二聚碳酸酯樹脂中,及包括在共聚碳酸酯樹脂中的以化學式1表示之重複單元可具有等於或不同於包括在第一和第二聚碳酸酯樹脂中的以化學式1表示之重複單元的結構之結構。
在化學式1中,R1至R4可各自獨立地為氫、甲基、氯基、或溴基。
另外,Z1較佳可為未經取代或經苯基取代之直鏈或支鏈C1-10伸烷基,且更佳地,亞甲基、乙烷-1,1-二基、丙烷-2,2-二基、丁烷-2,2-二基、1-苯基乙烷-1,1-二基或二苯基亞甲基。此外,Z1較佳可為環己烷-1,1-二基、O、S、SO、SO2、或CO。
較佳地,以化學式1表示之重複單元可衍生自一或多種選自由下列所組成群組之芳族二醇化合物:雙(4-羥基苯基)甲烷、雙(4-羥基苯基)醚、雙(4-羥基苯基)碸、雙(4-羥基苯基)亞碸、雙(4-羥基苯基)硫醚、雙(4-羥基苯基)酮、1,1-雙(4-羥基苯基)乙烷、雙酚A、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)環己烷、2,2-雙(4-羥基-3,5-
二溴苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)丙烷、2,2-雙(4-羥基-3-溴苯基)丙烷、2,2-雙(4-羥基-3-氯苯基)丙烷、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥基-3,5-二甲基苯基)丙烷、1,1-雙(4-羥基苯基)-1-苯基乙烷、雙(4-羥基苯基)二苯基甲烷、及α,ω-雙[3-(鄰-羥基苯基)丙基]聚二甲基矽氧烷。
如本文所用,'衍生自芳族二醇化合物'意指芳族二醇化合物之羥基和碳酸酯前驅物反應而形成以化學式1表示之重複單元。
例如,當雙酚A(即,芳族二醇化合物)和三光氣(即碳酸酯前驅物)聚合時,以化學式1表示之重複單元係以下示化學式1-1表示:
作為碳酸酯前驅物,可使用一或多種選自由下列所組成之群組:碳酸二甲酯、碳酸二乙酯、碳酸二丁酯、碳酸二己酯、碳酸二苯酯、碳酸二甲苯酯、雙(氯苯基)碳酸酯、碳酸二間-甲苯酚基酯、碳酸二萘酯、碳酸雙(二苯基)酯、光氣、三光氣、雙光氣、溴光氣和雙鹵甲酸酯。較佳地,可使用三光氣或光氣。
同時,共聚碳酸酯樹脂可另外包括以化學式3和4表
示之重複單元,其中該以化學式3和4表示之重複單元,其具有特定聚有機矽氧烷結構,可被引入共聚碳酸酯樹脂中以改良各種物理性質諸如耐化學性、低溫衝擊強度、YI值、等等。
在化學式3中,各X1較佳可獨立地為C2-10伸烷基,更佳為C2-4伸烷基及最佳為丙烷-1,3-二基。
且,較佳地,各R5可獨立地為氫、甲基、乙基、丙基、3-苯基丙基、2-苯基丙基、3-(環氧乙烷基甲氧基)丙基、氟基、氯基、溴基、碘基、甲氧基、乙氧基、丙氧基、烯丙基、2,2,2-三氟乙基、3,3,3-三氟丙基、苯基、或萘基。此外,各R5較佳可獨立地為C1-10烷基,更佳為C1-6烷基,仍更佳為C1-3烷基及最佳為甲基。
此外,較佳地,n可為10或更大、15或更大、20或更大、25或更大、30或更大、31或更大,或32或更大;且不大於50、不大於45、不大於40、不大於39、不大於38、或不大於37的整數。
在化學式4中,各X2較佳可獨立地為C2-10伸烷基,更佳為C2-6伸烷基及最佳為伸異丁基。
此外,較佳地,Y1可為氫。
另外,較佳地,各R14獨立地為氫、甲基、乙基、丙基、3-苯基丙基、2-苯基丙基、3-(環氧乙烷基甲氧基)丙基、氟基、氯基、溴基、碘基、甲氧基、乙氧基、丙氧基、烯丙基、2,2,2-三氟乙基、3,3,3-三氟丙基、苯基、或萘基。此外,各R14較佳可獨立地為C1-10烷基,更佳為
C1-6烷基,仍更佳為C1-3烷基,及最佳為甲基。
此外,較佳地,m可為40或更大、45或更大、50或更大、55或更大、56或更大、57或更大,或58或更大;且不大於80、不大於75、不大於70、不大於65、不大於64、不大於63,或不大於62之整數。
以化學式3表示之重複單元和以化學式4表示之重複單元係分別衍生自以化學式3-1表示之矽氧烷化合物和以化學式4-1表示之矽氧烷化合物:
在化學式3-1中,X1、R13和n係如前述所定義。
在化學式4-1中,X2、Y1、R14和m係如前述所定義。
如本文所用,'衍生自矽氧烷化合物'意指'各個矽氧烷化合物之羥基和碳酸酯前驅物反應以形成以化學式3表示之重複單元和以化學式4表示之重複單元。另外,可用於
形成以化學式3和4表示之重複單元的碳酸酯前驅物係與針對可用於形成上述以化學式1表示之重複單元的碳酸酯前驅物所述者相同。
用於製備以化學式3-1表示之矽氧烷化合物和以化學式4-1表示之矽氧烷化合物之方法分別係以下列反應流程圖1和2表示:
在上述反應流程圖1中,X1'為C2-10烯基,及X1、R13和n係與如前述所定義者相同。
[反應流程圖2]
在上述反應流程圖2中,X2'為C2-10烯基,及X2、Y1、R14和m係與如前述所定義者相同。
在反應流程圖1和反應流程圖2中,反應較佳可在金屬觸媒存在下進行。作為金屬觸媒,較佳使用Pt觸媒。在此所使用之Pt觸媒可包括一或多種選自由下列所組成之群組:Ashby觸媒、Karstedt觸媒、Lamoreaux觸媒、Speier觸媒、PtCl2(COD)、PtCl2(苯甲腈)2和H2PtBr6。金屬觸媒之使用量以100重量份的以化學式7或9表示之化合物為基準計可為0.001重量份或更大、0.005重量份或更大、或0.01重量份或更大;且不大於1重量份、不大於0.1重量份、或不大於0.05重量份。
另外,反應溫度較佳為80至100℃。另外,反應時間較佳為1至5小時。
此外,以化學式7或9表示之化合物可藉由使有機二矽氧烷和有機環矽氧烷在酸觸媒存在下反應而製備,及n
和m可藉由調整反應物的量來調整。反應溫度較佳為50至70℃。另外,反應時間較佳為1至6小時。
作為有機二矽氧烷,可使用一或多種選自由下列所組成之群組:四甲基二矽氧烷、四苯基二矽氧烷、六甲基二矽氧烷和六苯基二矽氧烷。此外,作為有機環矽氧烷可,例如可使用有機環四矽氧烷。有機環四矽氧烷之實例可包括八甲基環四矽氧烷和八苯基環四矽氧烷、等等。
有機二矽氧烷之使用量以100重量份的有機環矽氧烷為基準計可為0.1重量份或更大,或2重量份或更大;且不大於10重量份或不大於8重量份。
作為酸觸媒,可使用一或多種選自由下列所組成之群組:H2SO4、HClO4、AlCl3、SbCl5、SnCl4和酸性白土(漂白土)。另外,酸觸媒之使用量以100重量份的有機環矽氧烷為基準計可為0.1重量份或更大,0.5重量份或更大,或1重量份或更大;且不大於10重量份,不大於5重量份,或不大於3重量份。
藉由調整同時包括在共聚碳酸酯樹脂中的以化學式3和4表示之重複單元的量,可同時且適當地改良物理性質諸如耐化學性、衝擊強度、YI值、等等。為此目的,以化學式3和4表示之重複單元之間的重量比可從1:99至99:1。較佳地,重量比係從3:97至97:3,從5:95至95:5,從10:90至90:10,或從15:85至85:15,及更佳為從20:80至80:20。重複單元之重量比可對應於矽氧烷化合物(例如以化學式3-1表示之矽氧烷化
合物和以化學式4-1表示之矽氧烷化合物)的重量比。
較佳地,以化學式3表示之重複單元可以下示化學式3-2表示:
在化學3-2式中,R13和n係如前述所定義。較佳地,R13可為甲基。
此外,較佳地,以化學式4表示之重複單元可以下示化學式4-2表示:
在化學式4-2中,R14和m係如前述所定義。較佳地,R14可為甲基。
此外,上述共聚碳酸酯樹脂可包括各個以化學式1、3及4表示之重複單元以使以化學式1表示之重複單元和以化學式3表示之重複單元和以化學式4表示之重複單元的重量比為從1:0.001至1:0.5,較佳地,從1:0.005至1:0.3,及更佳地,從1:0.01至1:0.2。重複單元的
重量比可對應於用於形成以化學式1表示之重複單元芳族二醇化合物和用於形成和用於形成以化學式3表示之重複單元和以化學式4表示之重複單元的矽氧烷化合物之重量比。
作為共聚碳酸酯樹脂包括於上述重量比之各個重複單元,根據示例性實施態樣之共聚碳酸酯樹脂和樹脂組成物可具有極佳低溫衝擊強度、耐化學性和低YI值,且與將描述於下之第一聚碳酸酯樹脂的協同效應亦可被最佳化,致使根據示例性實施態樣之樹脂組成物可具有更優越的流動性和薄膜模塑性。
較佳地,包括以化學式1、3及4表示之重複單元的共聚碳酸酯樹脂可為隨機共聚物。此外,如上所述之共聚碳酸酯樹脂可藉由一種包括下列步驟之製備方法製備:聚合二或多種對應於各個重複單元之芳族二醇化合物、碳酸酯前驅物及二或多種矽氧烷化合物。芳族二醇化合物、碳酸酯前驅物及矽氧烷化合物係與如先前所述者相同。
在聚合之時,矽氧烷化合物之使用量以芳族二醇化合物、碳酸酯前驅物和矽氧烷化合物之總共100wt%為基準計可為0.1wt%或更大,0.5wt%或更大,1wt%或更大,或1.5wt%或更大;且不大於20wt%,不大於10wt%,不大於7wt%,不大於5wt%,不大於4wt%,不大於3wt%,或不大於2wt%。
另外,芳族二醇化合物之使用量以芳族二醇化合物、碳酸酯前驅物和矽氧烷化合物之總共100wt%為基準計可
為40wt%或更大,50wt%或更大,或55wt%或更大;且不大於80wt%,不大於70wt%,或不大於65wt%。
碳酸酯前驅物之使用量以二種芳族二醇化合物、碳酸酯前驅物和矽氧烷化合物之總共100wt%為基準計可為10wt%或更大,20wt%或更大、或30wt%或更大;且不大於60wt%,不大於50wt%,或不大於40wt%。
另外,關於聚合方法,可使用界面聚合法作為一個實例。在此情況下,聚合反應可在大氣壓於低溫下進行,且可容易控制分子量。界面聚合較佳可在酸黏合劑和有機溶劑存在下進行。再者,界面聚合可包括(例如)進行預聚合,然後添加偶合劑和再次進行聚合之步驟。在此情況下,可獲得具有高分子量的共聚碳酸酯。
不特別限制界面聚合中所使用的材料,只要彼等可使用於聚碳酸酯的聚合中即可。可根據需要控制其使用量。
酸黏合劑可包括(例如)鹼金屬氫氧化物諸如氫氧化鈉、氫氧化鉀、或類似者、或胺化合物諸如吡啶、或類似者。
不特別限制該有機溶劑,只要其為通常可使用於聚碳酸酯的聚合之溶劑即可。作為一個實例,可使用鹵化烴諸如二氯甲烷或氯苯、或類似者。
另外,在界面聚合期間,反應加速劑(例如)三級胺化合物諸如三乙胺、溴化四正丁銨和溴化四正丁鏻、或類似者、或四級銨化合物或四級鏻化合物、或類似者可進一步用於加速反應。
在界面聚合中,反應溫度較佳可為從0至40℃和反應時間較佳可為從10分鐘至5小時。另外,在界面聚合反應期間,pH較佳保持在9或更高、或11或更高。
此外,在界面聚合反應期間,可另外使用分子量調節劑。分子量調節劑可在聚合引發之前、聚合引發期間、或聚合引發之後添加。
作為分子量調節劑,可使用單烷基酚。作為一個實例,單烷基酚可為一或多種選自由下列所組成之群組:對三級丁基酚、對-異丙苯基酚、癸基酚、十二基酚、十四基酚、十六基酚、十八基酚、二十基酚、二十二基酚和三十基酚。較佳地,單烷基酚可為對三級丁基酚。在此情況下,調節分子量控制的效果可很大。
分子量調節劑之包括量以100重量份的芳族二醇化合物為基準計可為(例如)0.01重量份或更大、0.1重量份或更大或1重量份,且不大於10重量份或更大、不大於6重量份、或不大於5重量份。在如上所述之範圍內,可獲得所要分子量。
同時,上述共聚碳酸酯樹脂可具有1,000至100,000的重量平均分子量(g/mmol)。更佳地,重量平均分子量可為15,000或更大,16,000或更大,17,000或更大,18,000或更大,19,000或更大,20,000或更大,21,000或更大,22,000或更大,23,000或更大,24,000或更大,或25,000或更大;且不大於40,000,不大於39,000,不大於38,000,不大於37,000,不大於36,000,不大於
35,000,或不大於34,000。
(2)第一聚碳酸酯樹脂
根據示例性實施態樣之樹脂組成物可包括第一聚碳酸酯樹脂,其包括具有脂族伸烷基A的以化學式2表示之重複單元,和另外包括以化學式1表示之重複單元,根據需要,與上述共聚碳酸酯樹脂一起。作為如上所述之第一聚碳酸酯樹脂包括具有脂族基團的以化學式2表示之重複單元,此樹脂和包含彼之根據示例性實施態樣的樹脂組成物可具有高流動性、加工性、薄膜模塑性、等等。
因為選擇地包括在此第一聚碳酸酯樹脂的以化學式1表示之重複單元的說明提供於上述共聚碳酸酯樹脂的說明中,所以將省略對其的詳細說明。
同時,第一聚碳酸酯樹脂基本上可包括以化學式2表示之重複單元,其可區分第一聚碳酸酯樹脂與將描述於下之第二聚碳酸酯樹脂,即,一般芳族聚碳酸酯樹脂。在化學式2中,較佳地,R5至R12可各自獨立地為氫、甲基、氯基、或溴基。此外,較佳地,R5至R12可彼此相同。
另外,較佳地,Z1和Z2可各自獨立地為未經取代或經苯基取代之直鏈或支鏈C1-10伸烷基。更佳地,Z1和Z2可各自獨立地為亞甲基、乙烷-1,1-二基、丙烷-2,2-二基、丁烷-2,2-二基、1-苯基乙烷-1,1-二基或二苯基亞甲基。此外,較佳地,Z1和Z2可各自獨立地為環己烷-1,1-二基、O、S、SO、SO2、或CO。另外,較佳地,Z1和Z2可彼此
相同。
再者,較佳地,A可為直鏈或支鏈C1-10伸烷基。此外,A較佳可為直鏈C1-10伸烷基,更佳地,直鏈C3-9伸烷基,且最佳佳地,伸辛基。
更具體地說,以化學式2表示之重複單元可以化學式2-1表示:
以化學式2表示之重複單元可藉由以下示化學式2-2表示之芳族二醇化合物和碳酸酯前驅物的反應形成。
在化學式2-2中,R5至R12、Z2、Z3和A係如前述所定義。
可用於形成以化學式2表示之重複單元的碳酸酯前驅物之說明係與針對可用於形成上述以化學式1表示之重複單元的碳酸酯前驅物所述者相同。
第一聚碳酸酯樹脂可包括以化學式1表示之重複單元
及以化學式2表示之重複單元致使具有較佳從1:0.001至1:0.3,更佳為從1:0.004至1:0.15,及最佳為從1:0.01至1:0.1的重量比。第一聚碳酸酯樹脂在上述範圍內可具有適當機械性質和高流動性。重量比可對應於用以形成以化學式1和2表示之重複單元的芳族二醇化合物之重量比。
同時,上述第一聚碳酸酯樹脂可具有1,000至100,000的重量平均分子量(g/mmol)。更佳地,該重量平均分子量可為15,000或更大,16,000或更大,17,000或更大,18,000或更大,19,000或更大,20,000或更大,21,000或更大,22,000或更大,23,000或更大,24,000或更大,或25,000或更大;且不大於40,000,不大於39,000,不大於38,000,不大於37,000,不大於36,000,不大於35,000,或不大於34,000。
在根據示例性實施態樣的以聚碳酸酯為基礎之樹脂組成物中,共聚碳酸酯樹脂和第一聚碳酸酯樹脂之含量可根據所要調整之組成物的物理性質改變。例如,根據示例性實施態樣之樹脂組成物中所包括的共聚碳酸酯樹脂之含量以100wt%根據示例性實施態樣之整個樹脂組成物為基準計可為從1至99wt%,從10至90wt%,從30至70wt%,或從40至60wt%,及第一聚碳酸酯樹脂之含量,除了共聚碳酸酯之含量的其餘部分,以100wt%根據示例性實施態樣之樹脂組成物為基準計可為(例如)從1至99wt%,從10至90wt%,從30至70wt%,或從40至60
wt%。
因此,可將根據示例性實施態樣之樹脂組成物的流動性和加工性(薄膜模製性)、衝擊強度諸如低溫衝擊強度、或類似者、耐化學性、YI值、等等最佳化。然而,在其中添加過量含量之共聚碳酸酯樹脂的情況下,樹脂組成物之透明度可能被惡化,或流動性可能不足,及改良耐熱性和衝擊強度的效果可能會達到臨界值或被相當地惡化。另外,在其中添加過量含量之第一聚碳酸酯樹脂的情況下,樹脂組成物之衝擊強度、耐化學性、等等可能不足。
同時,根據示例性實施態樣之樹脂組成物可另外包括對應於不包括以化學式2至4表示之重複單元但只包括以化學式1表示之重複單元的一般芳族聚碳酸酯樹脂之第二聚碳酸酯樹脂。如上所述之第二聚碳酸酯樹脂可以第二聚碳酸酯樹脂不包括以化學式2至4表示之重複單元的事實而與共聚碳酸酯樹脂和第一聚碳酸酯樹脂區別。
第二聚碳酸酯樹脂中所包括的以化學式1表示之重複單元可具有等於或不同於相同類別中的以化學式1表示之重複單元的結構,包括在上述之共聚碳酸酯樹脂和第一聚碳酸酯樹脂中。
因為以化學式1表示之重複單元的說明係提供於共聚碳酸酯樹脂之說明中,藉由熟習該項技術者已知的方法可製備和提供對應於包括以化學式1表示之重複單元的一般芳族聚碳酸酯樹脂之第二聚碳酸酯樹脂,所以將省略其額外描述。
如上所述之第二聚碳酸酯樹脂的適當含量可由熟知該項技術者根據所需的物理性質或目的加至根據示例性實施態樣之樹脂組成物。然而,第二聚碳酸酯樹脂可以上述共聚碳酸酯樹脂和第一聚碳酸酯樹脂之總共100重量份為基準計為5至100重量份之含量範圍涵括,致使不會抑制藉由包括共聚碳酸酯樹脂和第一聚碳酸酯樹脂所獲得之根據示例性實施態樣的樹脂組成物之極佳物理性質和效果。
根據ASTM D256(1/8吋,缺口衝擊(Notched Izod))在23℃下測得之根據示例性實施態樣的上述樹脂組成物之室溫衝擊強度可為從500至1100J/m。更佳地,室溫衝擊強度(J/m)可為650或更大,700或更大,或750或更大。此外,室溫衝擊強度(J/m)越高,則越優越,使得溫衝擊強度(J/m)沒有上限,但室溫衝擊強度(J/m)可為例如不大於1050,或不大於1000。
此外根據ASTM D256(1/8吋,缺口衝擊)在-30℃下測得之根據示例性實施態樣的樹脂組成物之低溫衝擊強度可從350至1,000J/m。更佳地,低溫衝擊強度(J/m)可為450或更大、550或更大、650或更大,或680或更大。此外,低溫衝擊強(J/m)越高,則越優越,使得低溫衝擊強度(J/m)沒有上限,但低溫衝擊強度(J/m)可為例如不大於990、或不大於980。
根據ASTM D1925測得之根據示例性實施態樣的樹脂組成物之YI值可為不大於3。更佳地,YI值可為不大於2.5,不大於2,不大於1.99,或不大於1.98。此外,因為
YI值越低,則越優異,所以YI值沒有下限,但例如,YI值可為0.5或更大,1或更大或1.5或更大。
此外,根據ASTM D 1238(300℃,1.2kg條件)測得之根據示例性實施態樣的樹脂組成物之流動性可為從5至20g/10min。更佳地,流動性(g/10min)可為5.5或更大、6或更大,或6.5或更大;且不大於19、不大於18、不大於17、不大於16、不大於15,或不大於14。
同時,本發明之另一示例性實施態樣提供含有根據上述示例性實施態樣的以聚碳酸酯為基礎之樹脂組成物的模製物。
較佳地,模製物可為射出模製物。此外,該模製物可進一步包含(例如)一或多種選自由下列所組成之群組:抗氧化劑、熱穩定劑、光穩定劑、塑化劑、抗靜電劑、成核劑、阻燃劑、潤滑劑、衝擊增強劑、螢光增白劑、紫外線吸收劑、顏料和染料。
用於製備模製物之方法可包含下列之步驟:使用混合器混合根據示例性實施態樣之樹脂組成物和添加劑諸如抗氧化劑或類似物,用擠壓機將混合物擠壓模製以製造粒料,乾燥該粒料及然後用射出模製機射出乾燥的粒料。
如上所述,根據本發明之實施態樣,可提供除衝擊強度、耐化學性,及YI值之外,其流動性、加工性、薄膜模塑性等亦經改良之以聚碳酸酯為基礎之樹脂組成物,及
其模製物。
以下,將提供本發明之較佳實施例以更好地理解本發明。然而,提供下列實施例僅用於舉例說明本發明,而不應被解釋為本發明受這些實施例限制。
製備例1:聚有機矽氧烷AP-30的製備
將42.5g(142.8mmmol)的八甲基環四矽氧烷和2.26g(16.8mmmol)的四甲基二矽氧烷彼此混合之後,將混合物以100重量份的八甲基環四矽氧烷為基準計與1重量份的酸性白土(DC-A3)一起放入3L燒瓶中,並在60℃下反應4小時。反應終止後,將反應產物用乙酸乙酯稀釋並使用矽藻土迅速過濾。當經由1H NMR確認時,如上所述獲得之未改質的聚有機矽氧烷的重複單元(n)為30。
將9.57g(71.3mmmol)的2-烯丙基酚和0.01g(50ppm)的Karstedt氏鉑觸媒加至所得末端未改質的聚有機矽氧烷,並在90℃下反應3小時。反應終止後,藉由在120℃和1托的條件下進行蒸發移除未反應的矽氧烷。如
上所述獲得之末端改質的聚有機矽氧烷命名為AP-30。AP-30為淡黃色油且當經由使用Varian500MHz的1H NMR確認時,重複單元(n)為30,且不需要進一步純化。
製備例2:聚有機矽氧烷MB-60的製備
將47.60g(160mmol)的八甲基環四矽氧烷和1.5g(11mmol)的四甲基二矽氧烷彼此混合之後,將混合物以100重量份的八甲基環四矽氧烷為基準計與1重量份的酸性白土(DC-A3)一起放3L燒瓶中,並在60℃下反應4小時。反應終止後,將反應產物用乙酸乙酯稀釋並使用矽藻土迅速過濾。當經由1H NMR確認時,如上所述獲得之末端未改質的聚有機矽氧烷之重複單元(m)為60。
將6.13g(29.7mmol)的4-羥基苯甲酸3-甲基丁-3-烯基酯和0.01g(50ppm)的Karstedt氏鉑觸媒加至所得末端未改質的聚有機矽氧烷,並在90℃下反應3小時。反應終止後,藉由在120℃和1托的條件下進行蒸發移除未反應的矽氧烷。如上所述獲得之末端改質的聚有機矽氧烷命名為MB-60。MB-60為淡黃色油且當經由使用Varian500MHz的1H NMR確認時,重複單元(m)為60,且不需要進一步純化。
製備例3:共聚碳酸酯樹脂的製備1
在氮氛圍下將979.9g的雙酚A(BPA)、1,620g的32%NaOH水溶液、和7,500g的蒸餾水放入20L玻璃反應器中並確認BPA完全溶解之後,將3,670g的二氯甲烷、17.9g的對-三級丁基酚(PTBP)、79.3179g的預先製備之聚有機矽氧烷(AP-30)及8.8191g的製備例2之聚有機矽氧烷(MB-60)加入其中並與其混合(根據BPA使用9wt%的聚有機矽氧烷(AP-30+MB-60);形成以化學式1、3和4表示之重複單元致使具有與其對應的含量)。經1小時將其中溶解542.5g的三光氣之3,850g的二氯甲烷滴加至其中。在此情況下,將NaOH水溶液之PH保持在12。在滴加完成後,將混合物老化15分鐘,及將195.7g的三乙胺溶解在二氯甲烷中並加至其中。10分鐘之後,用1N鹽酸水溶液將pH調整至3,及接著將生成物用蒸餾水洗滌三次。其後,分離二氯甲烷相,及在甲醇中沉澱,藉此獲得呈粉末之聚碳酸酯樹脂(Mw:34000)。
製備例4:共聚碳酸酯樹脂的製備2
在氮氛圍下將979.9g的雙酚A(BPA)、1,620g的32%NaOH水溶液、和7,500g的蒸餾水放入20L玻璃反應器中並確認BPA完全溶解之後,將3,670g的二氯甲烷、17.9g的對-三級丁基酚(PTBP)、83.7814g的預先製備之聚有機矽氧烷(AP-30)和4.4096g的製備例2之聚有機矽氧烷(MB-60)加入其中並與其混合(根據BPA使用9wt%的
聚有機矽氧烷(AP-30+MB-60);形成以化學式1、3和4表示之重複單元致使具有與其對應的含量)。經1小時將其中溶解542.5g的三光氣之3,850g的二氯甲烷滴加至其中。在此情況下,將NaOH水溶液之PH保持在12。在滴加完成後,將混合物老化15分鐘,及將195.7g的三乙胺溶解在二氯甲烷中並加至其中。10分鐘之後,用1N鹽酸水溶液將pH調整至3,及接著將生成物用蒸餾水洗滌三次。其後,分離二氯甲烷相,及在甲醇中沉澱,藉此獲得呈粉末之聚碳酸酯樹脂(Mw:34000)。
製備例5:共聚碳酸酯樹脂的製備3
在氮氛圍下將979.9g的雙酚A(BPA)、1,620g的32%NaOH水溶液、和7,500g的蒸餾水放入20L玻璃反應器中並確認BPA完全溶解之後,將3,670g的二氯甲烷、17.9g的對-三級丁基酚(PTBP)、52.914g的預先製備之聚有機矽氧烷(AP-30)、和5.88g的製備例2之聚有機矽氧烷(MB-60)加入其中並與其混合(根據BPA使用6wt%的聚有機矽氧烷(AP-30+MB-60);形成以化學式1、3和4表示之重複單元致使具有與其對應的含量)。經1小時將其中溶解542.5g的三光氣之3,850g的二氯甲烷滴加至其中。在此情況下,將NaOH水溶液之PH保持在12。在滴加完成後,將混合物老化15分鐘,及將195.7g的三乙胺溶解在二氯甲烷中並加至其中。10分鐘之後,用1N鹽酸水溶液將pH調整至3,及接著將生成物用蒸餾水洗滌三
次。其後,分離二氯甲烷相,及在甲醇中沉澱,藉此獲得呈粉末之聚碳酸酯樹脂(Mw:34000)。
製備例6:共聚碳酸酯樹脂的製備4
在氮氛圍下將979.9g的雙酚A(BPA)、1,620g的32%NaOH水溶液、和7,500g的蒸餾水放入20L玻璃反應器中並確認BPA完全溶解之後,將3,670g的二氯甲烷、17.9g的對-三級丁基酚(PTBP)、和88.191g的預先製備之聚有機矽氧烷(AP-30)加入其中並與其混合(根據BPA使用9wt%的聚有機矽氧烷(AP-30);形成以化學式1和3表示之重複單元致使具有與其對應的含量)。經1小時將其中溶解542.5g的三光氣之3,850g的二氯甲烷滴加至其中。在此情況下,將NaOH水溶液之PH保持在12。在滴加完成後,將混合物老化15分鐘,及將195.7g的三乙胺溶解在二氯甲烷中並加至其中。10分鐘之後,用1N鹽酸水溶液將pH調整至3,及接著將生成物用蒸餾水洗滌三次。其後,分離二氯甲烷相,及在甲醇中沉澱,藉此獲得呈粉末之聚碳酸酯樹脂(Mw:34000)。
製備例7:第一聚碳酸酯樹脂的製備1
在氮氛圍下將979.9g的雙酚A(BPA)、1,620g的32%NaOH水溶液、和7,500g的蒸餾水放入20L玻璃反應器中並確認BPA完全溶解之後,將3,670g的二氯甲烷、17.9g的對-三級丁基酚(PTBP)和7.81g的預先製備之雙
(4-(2-(4-羥基苯基)丙-2-基)苯基)十二烷二酸酯(BPDA)加入其中並與其混合(根據BPA使用0.8wt%的BPDA;形成以化學式1和2表示之重複單元致使具有與其對應的含量)。經1小時將其中溶解542.5g的三光氣之3,850g的二氯甲烷滴加至其中。在此情況下,將NaOH水溶液之PH保持在12。在滴加完成後,將混合物老化15分鐘,及將195.7g的三乙胺溶解在二氯甲烷中並加至其中。10分鐘之後,用1N鹽酸水溶液將pH調整至3,及接著將生成物用蒸餾水洗滌三次。其後,分離二氯甲烷相,及在甲醇中沉澱,藉此獲得呈粉末之聚碳酸酯樹脂(Mw:34000)。
製備例8:第一聚碳酸酯樹脂的製備2
在氮氛圍下將968.9g的雙酚A(BPA)、1,620g的32%NaOH水溶液、和7,500g的蒸餾水放入20L玻璃反應器中並確認BPA完全溶解之後,將3,670g的二氯甲烷、17.9g的對-三級丁基酚(PTBP)、和29.32g的預先製備之雙(4-(2-(4-羥基苯基)丙-2-基)苯基)十二烷二酸酯(BPDA)加入其中並與其混合(根據BPA使用3.0wt%的BPDA;形成以化學式1和2表示之重複單元致使具有與其對應的含量)。經1小時將其中溶解542.5g的三光氣之3,850g的二氯甲烷滴加至其中。在此情況下,將NaOH水溶液之PH保持在12。在滴加完成後,將混合物老化15分鐘,及將195.7g的三乙胺溶解在二氯甲烷中並加至其中。10
分鐘之後,用1N鹽酸水溶液將pH調整至3,及接著將生成物用蒸餾水洗滌三次。其後,分離二氯甲烷相,及在甲醇中沉澱,藉此獲得呈粉末之聚碳酸酯樹脂(Mw:34000)。
製備例9:第一聚碳酸酯樹脂的製備3
在氮氛圍下將943.7g的雙酚A(BPA)、1,620g的32%NaOH水溶液、和7,500g的蒸餾水放入20L玻璃反應器中並確認BPA完全溶解之後,將3,670g的二氯甲烷、17.9g的對-三級丁基酚(PTBP)、和96.34g的預先製備之雙(4-(2-(4-羥基苯基)丙-2-基)苯基)十二烷二酸酯(BPDA)加入其中並與其混合(根據BPA使用10.0wt%的BPDA;形成以化學式1和2表示之重複單元致使具有與其對應的含量)。經1小時將其中溶解542.5g的三光氣之3,850g的二氯甲烷滴加至其中。在此情況下,將NaOH水溶液之PH保持在12。在滴加完成後,將混合物老化15分鐘,及將195.7g的三乙胺溶解在二氯甲烷中並加至其中。10分鐘之後,用1N鹽酸水溶液將pH調整至3,及接著將生成物用蒸餾水洗滌三次。其後,分離二氯甲烷相,及在甲醇中沉澱,藉此獲得呈粉末之聚碳酸酯樹脂(Mw:34000)。
製備例10:聚碳酸酯樹脂的製備4
在氮氛圍下將979.9g的雙酚A(BPA)、1,620g的
32%NaOH水溶液、和7,500g的蒸餾水放入20L玻璃反應器中並確認BPA完全溶解之後,將3,670g的二氯甲烷和17.9g的對-三級丁基酚(PTBP)加入其中並與其混合。經1小時將其中溶解542.5g的三光氣之3,850g的二氯甲烷滴加至其中。在此情況下,將NaOH水溶液之PH保持在12。在滴加完成後,將混合物老化15分鐘,及將195.7g的三乙胺溶解在二氯甲烷中並加至其中。10分鐘之後,用1N鹽酸水溶液將pH調整至3,及接著將生成物用蒸餾水洗滌三次。其後,分離二氯甲烷相,及在甲醇中沉澱,藉此獲得呈粉末之聚碳酸酯樹脂(Mw:34000)。
實施例1至5和比較例1至5:以聚碳酸酯為基礎之樹脂組成物和其模製物的製備
根據下表1中所說明之組成物製備共聚碳酸酯樹脂和聚碳酸酯樹脂。另外,以1重量份的樹脂混合物為基準計,將0.050重量份的參(2,4-二-三級丁基苯基)亞磷酸酯、0.010重量份的十八基-3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯、及0.030重量份的四硬脂酸季戊四醇酯加入其中,並使用具備排氣孔之Φ30mm雙螺桿擠壓機將所得混合物造粒,及使用N20C射出模製機(JSW Co.)在300℃的機筒溫度和80℃的模具溫度射出模製,藉此製備所要試樣。
實驗例:以聚碳酸酯為基礎之樹脂組成物和射出試樣之特性的確認
使用PC標準和Agilent 1200系列之以GPC測量實施例和比較例中所製備之共聚碳酸酯樹脂和聚碳酸酯樹脂的重量平均分子量。
此外,藉由下列方法測量實施例和比較例中所得之組成物和射出試樣之物理性質,且結果係說明於下表2中。
1)室溫衝擊強度:根據ASTM D256(1/8吋,缺口衝擊(Notched Izod))在23℃下測量。
2)低溫衝擊強度:根據ASTM D256(1/8吋,缺口衝擊)在-30℃下測量。
3)YI(黃色指數):在300℃下射出模製試樣(寬度/長度/厚度=60mm/40mm/3mm),及接著藉由使用Color-Eye 7000A(X-rite Inc.)根據ASTM D1925在下列條件下測量YI(黃色指數)。
- 測量溫度:室溫(23℃)
- 孔徑尺寸:大面積的視野
測量方法:在螺旋範圍(360nm至750nm)內測量透射率
4)流動性(MI):根據ASTM D1238測量(300℃,1.2kg條件)。
參照表2,可確認:在實施例1至5中,同時呈現出高室溫衝擊強度和低溫衝擊強度、低YI值、及較高流動
性(MI)。反之,可確認:在比較例1、3和5中,低溫衝擊強度為低的。特別地,如比較例5中所說明,可確認:在其中共聚碳酸酯樹脂之結構與實施例不同的情形下,低溫衝擊強度被惡化。
另外,可確認:比較例2和4,流動性差,相較於實施例,YI值高,及在比較例4中,低溫衝擊強度也不足。
Claims (18)
- 一種以聚碳酸酯為基礎之樹脂組成物,其包含:共聚碳酸酯樹脂,其包括以下示化學式1表示之重複單元、以下示化學式3表示之重複單元、及以下示化學式4表示之重複單元;及第一聚碳酸酯樹脂,其包括以下示化學式2表示之重複單元:
- 如申請專利範圍第1項之以聚碳酸酯為基礎之樹脂組成物,其中:該第一聚碳酸酯樹脂另外包括以化學式1表示之重複單元。
- 如申請專利範圍第1項之以聚碳酸酯為基礎之樹脂組成物,其另外包含只包括以化學式1表示之重複單元的第二聚碳酸酯樹脂。
- 如申請專利範圍第1項之以聚碳酸酯為基礎之樹脂組成物,其中:該第一和第二聚碳酸酯樹脂及該共聚碳酸酯樹脂分別具有1,000至100,000之重量平均分子量。
- 如申請專利範圍第1至3項中任一項之以聚碳酸酯為基礎之樹脂組成物,其中:該以化學式1表示之重複單元係衍生自一或多種選自由下列所組成群組之芳族二醇化合物:雙(4-羥基苯基)甲烷、雙(4-羥基苯基)醚、雙(4-羥基苯基)碸、雙(4-羥基苯 基)亞碸、雙(4-羥基苯基)硫醚、雙(4-羥基苯基)酮、1,1-雙(4-羥基苯基)乙烷、雙酚A、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)環己烷、2,2-雙(4-羥基-3,5-二溴苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)丙烷、2,2-雙(4-羥基-3-溴苯基)丙烷、2,2-雙(4-羥基-3-氯苯基)丙烷、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥基-3,5-二甲基苯基)丙烷、1,1-雙(4-羥基苯基)-1-苯基乙烷、雙(4-羥基苯基)二苯基甲烷、及α,ω-雙[3-(鄰-羥基苯基)丙基]聚二甲基矽氧烷。
- 如申請專利範圍第1至3項中任一項之以聚碳酸酯為基礎之樹脂組成物,其中:該以化學式1表示之重複單元係以下示化學式1-1表示:
- 如申請專利範圍第1項之以聚碳酸酯為基礎之樹脂組成物,其中:R5至R12各自獨立地為氫、甲基、氯基、或溴基。
- 如申請專利範圍第1至3項中任一項之以聚碳酸酯為基礎之樹脂組成物,其中:Z1和Z2各自獨立地為未經取代或經苯基取代之直鏈 或支鏈C1-10伸烷基、環己烷-1,1-二基、O、S、SO、SO2、或CO。
- 如申請專利範圍第1項之以聚碳酸酯為基礎之樹脂組成物,其中:A為直鏈C1-10伸烷基。
- 如申請專利範圍第1項之以聚碳酸酯為基礎之樹脂組成物,其中:該以化學式2表示之重複單元係以化學式2-1表示:
- 如申請專利範圍第2項之以聚碳酸酯為基礎之樹脂組成物,其中:該第一聚碳酸酯樹脂包括重量比為1:0.001至1:0.3的以化學式1表示之重複單元和以化學式2表示之重複單元。
- 如申請專利範圍第1項之以聚碳酸酯為基礎之樹脂組成物,其中:該共聚碳酸酯樹脂包括各個重複單元使得該以化學式1表示之重複單元與該以化學式3和4表示之重複單元的重量總和之重量比為1:0.001至1:0.5。
- 如申請專利範圍第1項之以聚碳酸酯為基礎之樹 脂組成物,其中:該以化學式3表示之重複單元係以化學式3-2表示:
- 如申請專利範圍第12項之以聚碳酸酯為基礎之樹脂組成物,其中:R13為甲基。
- 如申請專利範圍第1項之以聚碳酸酯為基礎之樹脂組成物,其中:該以化學式4表示之重複單元係以化學式4-2表示:
- 如申請專利範圍第14項之以聚碳酸酯為基礎之樹脂組成物,其中:R14為甲基。
- 如申請專利範圍第1項之以聚碳酸酯為基礎之樹脂組成物,其中:其包括1至99wt%的該共聚碳酸酯樹脂,及 1至99wt%的該第一聚碳酸酯樹脂。
- 一種模製物,其包含如申請專利範圍第1項之以聚碳酸酯為基礎之樹脂組成物。
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TWI707886B (zh) * | 2016-10-20 | 2020-10-21 | 南韓商Lg化學股份有限公司 | 聚碳酸酯樹脂組成物 |
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